TWI532751B - Inorganic oxide transparent fluid dispersion, resin composition for forming transparent composite, transparent composite and optical member - Google Patents

Description

Inorganic oxide transparent dispersion, resin composition for forming transparent composite, transparent composite, and optical member

The present invention relates to an inorganic oxide transparent dispersion, a resin composition for forming a transparent composite, a transparent composite, and an optical member, and more particularly, in particular, a filler suitable for use as an organic resin for an inorganic oxide is used. An inorganic oxide transparent dispersion which can improve the optical properties and mechanical properties of the resin while maintaining the transparency of the resin, a resin composition for forming a transparent composite containing the inorganic oxide transparent dispersion and the resin, and a transparent composite formed therefrom A transparent composite formed of a resin composition and an optical member including the transparent composite.

The present application claims priority from Japanese Patent Application No. 2011-188631, filed on Jan. 31, 2011 in

In general, in order to make an optical product an ideal design, optical components such as lenses, iridium, optical waveguides, and optical films constituting the optical system of the optical product have transparency, high refractive index, and wavelength dispersion of refractive index. Characteristics are important. In addition, it is important to have mechanical properties such as thermal characteristics such as thermal expansion of the environmental temperature change and mechanical strength of external force. Further, in the case of an optical film or the like, the adhesion to the substrate to which the optical film is placed is also important.

As the resin which can be used for the optical member, an organic resin such as an epoxy resin, an acrylic resin, a polyester resin or a polycarbonate resin can be generally used. Further, it is proposed to add inorganic oxide particles to the organic tree for the purpose of designing the optical and mechanical properties of the organic resins to be optimal. The lipid is a composite transparent composite.

The inorganic oxide particles to be added are suitably selected in accordance with the optical properties, thermal properties, and mechanical properties required for the transparent composite. For example, in the case where the refractive index of the organic resin is to be increased, a metal oxide such as zirconium or titania having a high refractive index can be selected.

In order to obtain the transparent composite in a uniform manner, in order to uniformly disperse the inorganic oxide particles in the transparent composite, first, the inorganic oxide particles are dispersed in a solvent to form an inorganic oxide dispersion, and the inorganic oxide is dispersed. The dispersion is mixed with a resin to form a resin composition for forming a transparent composite.

Then, the resin composition for forming a transparent composite is introduced into a molding die, and each of the molding dies is dried by heating or under reduced pressure to remove the solvent of the resin composition, and then the resin is cured by heating or irradiation with ultraviolet rays or the like. A transparent composite of the specified shape is obtained.

Further, the resin composition for forming a transparent composite is coated on a transparent plastic substrate by spin coating or screen printing, and the resin is composed by drying or drying each transparent plastic substrate under reduced pressure. The solvent of the substance is removed, and then the resin is cured by heating or irradiation with ultraviolet rays or the like to obtain a specified film-like transparent composite.

In order to prevent the water absorption of the resin due to the change in humidity in the environment and to impair the dimensional stability, the transparent composite uses a low-polarity organic resin having a low non-aqueous polarity.

On the other hand, in order to uniformly disperse the inorganic oxide particles in such a low-polarity organic resin without uneven distribution, it is necessary to ensure inorganic oxide particles. The surface of the sub-substrate has an interfacial affinity with the low-polarity organic resin. Therefore, the inorganic oxide particles are subjected to surface modification so that the surface thereof has the same low polarity as the low-polarity organic resin.

When the transparent composite is applied to an optical member, in order to obtain a more transparent composite, the dispersion state of the inorganic oxide particles in the transparent composite needs to be closer to a monodisperse state, and for this reason, it is required to be organic with low polarity. The dispersibility of the inorganic oxide particles in the resin-mixed inorganic oxide dispersion is improved, and the transparency of the inorganic oxide dispersion is also required to be improved.

In order to obtain a transparent composite having such characteristics, it is proposed to treat the surface of the metal oxide particles with a surface modifying agent having a reactive group, and to disperse the surface-modified metal oxide particles in a low amount such as toluene or methyl ethyl ketone. A dispersion or a curable composition in a polar solvent (see Patent Documents 1 to 3, etc.).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-195967

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-217242

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-269644

However, the dispersion liquid or the curable composition proposed in the prior patent documents 1 to 3 and the like have the following problems.

(1) In the case of using a low-polar solvent dispersion such as toluene or a curable composition, a low-polar solvent easily erodes a plastic substrate, and therefore, a transparent composite is produced. The conditions of the body, in particular, the type of the plastic substrate coated with the dispersion or the curable composition, the time when the plastic substrate contacts the low-polar solvent, the thickness of the transparent composite, and the heating temperature, etc. The problem of insufficient transparency of the composite.

(2) Since the surface of the metal oxide particles which can be used for the dispersion or the curable composition is treated with a surface modification agent having a low polarity, the surface of the surface-modified metal oxide particles is low in polarity. On the other hand, in the case of a highly polar solvent which does not easily erode the plastic substrate, there are alcohols, ethers and the like. Therefore, it is very difficult to uniformly disperse the low-polarity surface-modified metal oxide particles in a highly polar solvent which does not easily erode the plastic substrate, so that the low-polarity surface-modified metal oxide particles are dispersed in a highly polar solvent. The dispersibility of the surface-modified metal oxide particles in the obtained dispersion or the curable composition is inferior, and as a result, when the dispersion or the curable composition is used, there is a problem that a composite having high transparency cannot be obtained. .

The present invention has been made in view of the above circumstances, and an object thereof is to provide an inorganic oxidation which can maintain the transparency of a resin by uniformly dispersing inorganic oxide particles in a highly polar solvent while improving the optical properties and mechanical properties of the resin. The transparent dispersion liquid, the resin composition for forming a transparent composite, the transparent composite, and the optical member.

In order to solve the above problems, the inventors of the present invention conducted a thorough review and found that the inorganic oxide particles are enhanced for high polarity by adding a basic substance to a dispersion liquid containing inorganic oxide particles modified with a surface modifier and a highly polar solvent. The dispersibility of the solvent, 遂 completed the present invention.

In other words, the inorganic oxide transparent dispersion of the present invention contains inorganic oxide particles modified by a surface modifier and having an average dispersed particle diameter of 1 nm or more and 50 nm or less, which dissolves the resin and hardly erodes the resin. The high-polarity solvent of the resin and the alkaline substance, and the high-polarity solvent is any one or two of an alcohol and an ether.

The inorganic oxide particles are preferably one of a metal oxide particle and a non-metal oxide particle as a main component.

The resin composition for forming a transparent composite of the present invention contains the inorganic oxide transparent dispersion of the present invention and a resin.

The transparent composite system of the present invention is formed using the resin composition for forming a transparent composite of the present invention.

The optical member of the present invention comprises the transparent composite of the present invention.

According to the present invention, the inorganic oxide transparent dispersion liquid contains: an inorganic oxide particle modified by a surface modifier and having an average dispersed particle diameter of 1 nm or more and 50 nm or less, a resin which dissolves the resin and hardly erodes the hardened resin of the resin. A highly polar solvent and a basic substance, and the highly polar solvent is any one or two of an alcohol and an ether, so that the surface oxide-modified inorganic oxide particles in the presence of a basic substance can be improved. Dispersibility of highly polar solvents. Therefore, the inorganic oxide particles modified by the surface modifier can be well dispersed in a highly polar solvent, and as a result, by using the above inorganic oxide transparent dispersion, the production conditions of the transparent composite can be easily determined without being limited. A transparent composite excellent in stability and excellent in transparency is obtained.

The form of the inorganic oxide transparent dispersion liquid, the transparent composite-forming resin composition, the transparent composite, and the optical member for carrying out the present invention will be described below.

In addition, this form is a specific description for the purpose of understanding the invention well, and is not limited to the inventors unless otherwise specified.

[Inorganic oxide transparent dispersion]

The inorganic oxide transparent dispersion of the present embodiment contains inorganic oxide particles modified by a surface modifier and having an average dispersed particle diameter of 1 nm or more and 50 nm or less, which dissolves the resin and hardly erodes the resin. A highly polar solvent of a hardening resin and an alkaline substance.

[Inorganic oxide particles]

The inorganic oxide particles which can be used in the present embodiment are preferably one of metal oxide particles and non-metal oxide particles as a main component.

As the metal oxide particles, metal oxide particles generally used as a filler in a resin can be suitably used. For such metal oxide particles, for example, zirconium oxide (ZrO ₂ : zirconium oxide) or titanium oxide (TiO ₂ ) can be used. : titanium oxide), aluminum oxide (Al ₂ O ₃ : aluminum oxide (alumina)), iron oxide (Fe ₂ O ₃ , Fe ₃ O ₄ ), copper oxide (CuO), zinc oxide (ZnO), cerium oxide (Y ₂ O ₃ : yttria), cerium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ , MoO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), tantalum oxide _{(Ta 2 O 5, TaO 2} ), tungsten oxide (WO _3, WO _2), lead oxide (PbO), bismuth oxide (Bi ₂ O _3), cerium oxide (CeO _2: cerium oxide (ceria)), Cerium oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ) and the like.

As the non-metal oxide particles, for example, cerium oxide (SiO ₂ :silica) or boron oxide (B ₂ O ₃ ) which is generally used as a filler in a resin can be used.

These metal oxide particles and non-metal oxide particles may be used singly or in combination of two or more kinds.

Among the inorganic oxide particles, when the transparent composite is produced using the inorganic oxide transparent dispersion of the present embodiment, the obtained transparent composite has a higher refractive index, and is made of zirconium oxide (ZrO). ₂ : zirconium oxide) or titanium oxide (TiO ₂ : titanium oxide) is preferred.

When zirconium oxide (ZrO ₂ ) particles (zirconium oxide particles) are used, any of monoclinic zirconium oxide particles or tetragonal zirconium oxide particles, or monoclinic zirconium oxide particles and tetragonal zirconium oxide can be used. As the oxide particles, tetragonal zirconium oxide particles are preferred for the following reasons.

The reason why the tetragonal zirconium oxide particles are preferred is that when the fine particles are synthesized, the average dispersed particle diameter of the fine particles is less than, for example, 20 nm or less, and the tetragonal zirconium oxide particles are more conventionally known. It is more stable and has a high hardness, and the mechanical properties of the resin composite in which the tetragonal zirconium oxide particles are dispersed in the resin are improved, and the resin composite is combined with the case where the monoclinic zirconium oxide particles are added. The system exhibits higher toughness by a volume expansion called a martensitic transformation.

Further, cubic zirconium oxide particles may be contained as long as the desired characteristics are not lost.

The average particle diameter of the inorganic oxide particles in the inorganic oxide transparent dispersion is preferably 1 nm or more and 50 nm or less, more preferably 3 nm or more and 30 nm or less, and even more preferably 5 nm or more and 20 nm or less. .

If the average dispersed particle size is less than 1 nm, due to the inorganic oxide particles themselves On the other hand, if the average dispersed particle diameter exceeds 50 nm, the transparency of the transparent composite produced by using the inorganic oxide transparent dispersion may be deteriorated, so that it is not good.

Further, in the average dispersed particle diameter of the present embodiment, the particle diameter of the inorganic oxide particles in the inorganic oxide transparent dispersion liquid is measured by a dynamic light scattering method, and the cumulative volume fraction obtained is 50% by volume. Dispersed particle size (D50).

The content (% by mass) of the inorganic oxide particles in the inorganic oxide transparent dispersion is not particularly limited, and may be appropriately selected in order to obtain a transparent composite. In particular, it is more preferably 1% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, in order to improve the workability and to improve the production efficiency.

Since the inorganic oxide particles are required to ensure the interface affinity between the surface and the above resin, it is preferred to modify the surface of the inorganic oxide particles with a surface modifying agent.

The surface modifying agent is not particularly limited as long as it is a surface modifying agent which is excellent in compatibility with the above-mentioned resin, and examples thereof include a compound represented by the following formula (1).

R _x -Si-R' _4-x .........(1)

In the formula (1), R is a vinyl group, an allyl group, a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-propenyloxypropyl group, 3-methylpropenylpropyl, styryl, 3-aminopropyl, N-2(aminoethyl) 3-aminopropyl, N-phenyl-3-aminopropyl, 3 - mercaptopropyl group, 3-isocyanatopropyl ester, alkyl group having a carbon number of 1 or more and 20 or less, and a group of phenyl groups One or two or more selected from the group consisting of: R' is one or more selected from the group consisting of alkoxy group and ethoxy group having chlorine, a hydroxyl group, and a carbon number of 1 or more and 20 or less, and X is 0, or 1 or more and an integer of 4 or less.

Examples of such a surface modifier include a decane coupling agent, a titanium coupling agent, a modified polysilicon oxide, and the like, and examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl three. Chlorodecane, vinyltriphenoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyltrichlorodecane, 3-glycidoxypropyltriphenoxydecane, p-styryltrimethoxydecane, p-styryltriethoxydecane, p-styryltrichlorodecane, p-styryltriphenoxydecane , 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyltrichlorodecane, 3-propenylmethoxypropyltriphenyl Oxydecane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltrichlorodecane, 3 - methacryloxypropyltriphenyloxydecane, and the like.

Further, examples thereof include allyltrimethoxydecane, allyltriethoxydecane, allyltrichlorodecane, allyltriphenoxydecane, vinylethyldimethoxydecane, and vinylethylene B. Diethoxy decane, vinyl ethyl dichloro decane, vinyl ethyl diphenoxy decane, 3-glycidoxy propyl ethyl dimethoxy decane, 3-glycidoxy propyl three Ethyldiethoxydecane, 3-glycidoxypropylethyldichlorodecane, 3-glycidoxypropylethyldiphenoxydecane, p-styrylethyldimethoxydecane, P-styrylethyl diethoxy decane, p-styryl triethyl Chlorodecane, p-styrylethyldiphenoxydecane, 3-propenyloxypropylethyldimethoxydecane, 3-propenyloxypropylethyldiethoxydecane, 3-propene醯oxypropylethyldichlorodecane, 3-propenyloxypropylethyldiphenoxydecane, 3-methylpropenyloxypropylethyldimethoxydecane, 3-methylpropene醯oxypropylethyldiethoxydecane, 3-methylpropenyloxypropylethyldichlorodecane, 3-methylpropenyloxypropylethyldiphenoxydecane, allyl Ethyldimethoxydecane, allylethyldiethoxydecane, allylethyldichlorodecane, allylethyldiphenoxydecane, and the like.

Further, examples thereof include vinyl diethyl methoxy decane, vinyl diethyl ethoxy decane, vinyl diethyl chloro decane, vinyl diethyl phenoxy decane, and 3-glycidoxy propyl group. Diethylmethoxydecane, 3-glycidoxypropyldiethylethoxydecane, 3-glycidoxypropyldiethylchlorodecane, 3-glycidoxypropyldiethylbenzene Oxydecane, p-styryl diethyl methoxy decane, p-styryl diethyl ethoxy decane, p-styryl diethyl chloro decane, p-styryl diethyl phenoxy decane, 3-propenyloxypropyl diethylmethoxydecane, 3-propenyloxypropyldiethylethoxydecane, 3-propenyloxypropyldiethylchlorodecane, 3-propenepyrene Oxypropyl propyl phenoxy decane, 3-methyl propylene methoxy propyl diethyl methoxy decane, 3-methyl propylene methoxy propyl diethyl ethoxy decane, 3- Methyl propylene methoxypropyl diethyl chloro decane, 3-methyl propylene methoxy propyl diethyl phenoxy decane, allyl diethyl methoxy decane, allyl diethyl ethene Oxyl Alkyl, allyl diethyl Silane chloride, allyl diethylphenoxy Silane like.

Examples of the modified polyfluorene oxide include epoxy modified polyfluorene oxide, epoxy/polyether modified polyfluorene oxide, methacrylic modified polyfluorene oxide, phenol modified polyoxymethylene, and methyl styrene. The modified polyfluorene oxide, the acrylic modified polyoxymethylene, the alkoxy modified polyoxynium, the methyl hydrogenated polyoxygen, and the like.

The amount of modification of the surface of the inorganic oxide particles of the surface modifier is preferably as long as the compatibility between the obtained surface-modified inorganic oxide particles and the resin is good, and is not particularly limited, and particularly, In the case of the refractive index of the resin, in order to balance the transparency of the inorganic oxide transparent dispersion with the refractive index of the resin, the amount of the surface modifier is 5% by mass based on the total amount of the inorganic oxide particles. The above is preferably 100% by mass or less, more preferably 10% by mass or more and 50% by mass or less.

[High Polar Solvent]

It is preferable that the high-polarity solvent is an alcohol or an ether which is easy to dissolve the above-mentioned resin or a resin to be described later, and which is hard to erode the resin to be cured by heat curing or irradiation with ultraviolet rays or the like. Alcohols and ethers may be used alone or in combination of two or more.

Here, the "dissolved resin" means a resin which can be dissolved before being hardened by heat curing or irradiation with ultraviolet rays or the like. In other words, the "highly polar solvent of the hardened resin which dissolves the resin and hardly erodes the resin is not inferior", that is, "the solubility to the uncured curable resin is low, and the resin after the hardening is low. An aggressive, highly polar solvent."

Among them, in the case of alcohols, alcohols having a carbon number of 4 or less in the main chain are used. Preferably, for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropanol, butyl alcohol, second butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, Trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol, 2,3-butanediol, and the like. Among these, isopropyl alcohol is particularly preferred.

Examples of the ethers include ethylene glycol monomethyl ether (methionine), ethylene glycol monoethyl ether (ethyl acesulfame), propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Dipropylene glycol and the like are particularly preferred as propylene glycol monomethyl ether.

In particular, the alcohol may be used alone or in combination of two or more kinds.

In addition, the ether may be used alone or in combination of two or more kinds.

In addition, one or two or more kinds of the above various alcohols may be selected, and one or two or more kinds of the above various ethers may be selected, and these alcohols and ethers may be mixed and used as an alcohol/ether mixed solution.

[Alkaline substance]

The basic substance of the present embodiment is a substance containing a hydroxide, an ammonia, an amine, or the like of an alkali metal or an alkaline earth metal, and having a hydrogen ion index (pH) greater than 7 when dissolved in water. It can be, and is not particularly limited.

Examples of such a basic substance include calcium hydroxide, magnesium hydroxide, manganese hydroxide, iron hydroxide, zinc hydroxide, copper hydroxide, barium hydroxide, aluminum hydroxide, iron hydroxide, ammonia, ammonium hydroxide, An inorganic alkaline substance such as potassium hydroxide or sodium hydroxide.

In addition, there are also listed: methylamine, etheramine, ethylamine, trimethylamine, triethylamine, triethanolamine, N,N-diisopropylethylamine, piperidine, piperidine ,Morpholine, Quinuclidine, 1,4-dioxabicyclo[2.2.2]octane (DABCO), pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylamethylenediamine (TMEDA), Amines such as hexamethylenediamine, aniline, catecholamine, phenethylamine; 1,8-bis(dimethylamino)naphthalene (proton sponge), amine Alkanoic acid, amantadine, spermidine, spermine, and the like.

These inorganic basic substances, amines, and other basic substances may be used alone or in combination of two or more.

Among these, ammonia is preferred because it is easy to handle and does not easily remain as an impurity.

The alkaline substance is added in order to adjust the dispersibility of the inorganic oxide particles to the highly polar solvent and adjust the amount required.

The content of the basic substance in the inorganic oxide transparent dispersion of the present embodiment is preferably 0.01% by mass or more and preferably 10% by mass or less, and 0.03% by mass or more and 2% by mass or less or less based on the total amount of the inorganic oxide particles. For better.

When the content of the basic substance is less than 0.01% by mass based on the total amount of the inorganic oxide particles, the dispersibility of the inorganic oxide particles to the highly polar solvent cannot be improved, and on the other hand, with respect to the total amount of the inorganic oxide particles, Even if the content of the basic substance exceeds 10% by mass, the dispersion effect of the inorganic oxide particles is not significantly different, and it is an impurity, which is not preferable.

The inorganic oxide transparent dispersion of the present embodiment is composed of a base The substance can be well dispersed in the highly polar solvent by the surface-modified inorganic oxide particles.

Although the details of the mechanism by which such an effect can be obtained are not clear, for example, in the case of inorganic oxide particles surface-modified with a decane coupling agent, the following considerations can be made.

As shown in Fig. 1(a), the alkoxy group of the decane coupling agent 2 on the surface of the modified inorganic oxide particle 1 is hydrolyzed to a hydroxyl group (OH group), and the OH group is present by hydrogen bonding or dehydration condensation. The inorganic oxide particles 1 are chemically bonded to the unbonded portion (the portion of the OH group).

The alkaline substance 3 is added in a small amount to the dispersion of the inorganic oxide particles 1 dispersed in such a state, that is, as shown in the first (b) diagram, the OH group of the unbonded portion of the decane coupling agent 2 is proton-decomposed, and The polarity of this part is increased (OH→O-).

In such a manner, by making the decane coupling agent 2 of the surface-modified inorganic oxide particle 1 a part of the arsenal coupling agent 2' having an increased polarity, it is considered that it is improved in dispersibility with a highly polar solvent.

[Method for Producing Inorganic Oxide Transparent Dispersion]

By using an inorganic oxide particle which is modified by a surface modifying agent and having an average dispersed particle diameter of 1 nm or more and 50 nm or less, a highly polar solvent which hardens the resin by hardening the resin and hardly erodes the resin, and a basic substance uniformly The inorganic oxide transparent dispersion of the present embodiment can be easily obtained by mixing.

As the inorganic oxide particles, a powder having a primary particle diameter of 1 nm or more and 10 nm or less can be used, and the powders can be dispersed in a dispersion medium. Dispersion.

Here, a method of producing the inorganic oxide particles modified by the surface modifier will be described.

First, inorganic oxide particles are produced.

For example, a metal salt such as zirconium oxychloride octachloride or titanium trichloride is dissolved in a metal salt solution of pure water, and while stirring, a diluted aqueous ammonia solution is added to prepare a metal oxide precursor slurry.

Next, an aqueous solution of an inorganic salt such as sodium sulfate is added to the slurry while stirring to obtain a mixture. At this time, the amount of the inorganic salt added is 20 to 40% by mass based on the metal oxide equivalent value of the metal ion in the metal salt solution.

Next, the mixture is dried in the air at 100 ° C or higher and 150 ° C or lower for 24 hours or longer and 36 hours or shorter to obtain a solid matter.

Then, the solid matter is pulverized by an automatic mortar or the like, and fired in the air at 300 ° C or higher and 700 ° C or lower for 1 hour or longer and 6 hours or shorter, for example, at 500 ° C for 3 hours.

Next, the fired product was poured into pure water and stirred to obtain a slurry. Next, washing is performed to sufficiently remove the added inorganic salt, followed by drying. Thereby, a metal oxide particle of an inorganic oxide particle is obtained.

Next, an aqueous solution of water or alcohol is added to the metal oxide particles obtained above to form a slurry, and then the above surface modifying agent is added to the slurry and appropriately mixed. Thereby obtaining a surface modifier The inorganic oxide particles on the surface.

In this state, the surface-modified inorganic oxide particles are dispersed in the slurry or settled in the bottom of the slurry, so that the surface-modified inorganic oxide is subjected to solid-liquid separation or the like. The particles are recovered in the form of a solid. By drying the solid matter, inorganic oxide particles whose surface is modified with a surface modifier can be obtained.

Further, the alkaline substance may be mixed with the inorganic oxide particles and the highly polar solvent in the preparation of the inorganic oxide transparent dispersion, or may be obtained by adding the surface modifying agent to obtain surface-modified inorganic oxide particles. Add to.

In this case, since the amount of the alkaline substance is reduced due to solid-liquid separation or the like, the amount of the alkaline substance added to the slurry is adjusted in consideration of the reduced amount.

In the case where the slurry is added with a surface modifying agent and mixed, and a basic substance is added in the surface modification step, the addition of the basic substance to the metal oxide particles is 0.5% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less are preferable.

[Resin composition for forming a transparent composite]

The resin composition for forming a transparent composite of the present embodiment contains the resin composition of the inorganic oxide transparent dispersion of the present embodiment and a resin.

The resin may be any resin which can be mixed with a highly polar solvent in an uncured state, and is not particularly limited. For example, a melamine resin, a phenol resin, a polyester resin, an amine ester resin, or propylene can be used. An acid resin, a vinyl chloride resin, a polypropylene resin, a polycarbonate resin, a polyethylene terephthalate (PET) resin, an epoxy resin, or the like. Among these, an acrylic resin is preferred.

The content of the inorganic oxide particles of the resin composition for forming a transparent composite is preferably 10% by mass or more and 60% by mass or less, based on the total mass of the inorganic oxide particles and the resin.

When the content of the inorganic oxide particles is within the above range and is mixed with the resin, the properties of the inorganic oxide particles are imparted, and the workability in forming the composite described later is preferable, which is preferable.

In the resin composition for forming a transparent composite, an additive generally used, such as an organic solvent or a photoinitiator, may be added as needed.

The method of producing the resin composition for forming a transparent composite is not particularly limited as long as it is a method of uniformly mixing the inorganic oxide particle transparent dispersion of the present embodiment with a resin, and a conventional one can be used. Stirring method.

[transparent complex]

In the transparent composite system of the present embodiment, a composite which is transparent to visible light rays formed by the resin composition for forming a transparent composite of the present embodiment is used.

In the case where the thickness of the transparent composite is 30 μm, the transmittance of the wavelength region of 400 nm to 800 nm in the visible light region of the transparent composite is preferably 80% or more, more preferably 90% or more.

In the case of the transparent composite, for example, when a bulk body having a three-dimensional shape is produced, the transparent composite of the present embodiment can be formed. A method in which a resin composition is discharged into a mold having a predetermined shape, and then cured by irradiation or irradiation with ultraviolet rays or the like depending on the type of the resin.

In addition, when the coating film is produced, the resin composition for forming a transparent composite of the present embodiment is applied to a plastic substrate, and then heat hardening by heating or light curing by ultraviolet light or the like is performed as needed. Method, etc.

The plastic substrate is not particularly limited as long as it is a plastic substrate, and may be appropriately selected depending on the application. Examples of such a plastic substrate include an acrylic type, an acrylic type rubber containing a highly elastic acrylic rubber, an acrylic-styrene copolymer, polystyrene, polyethylene, polypropylene, polycarbonate, and polyparaphenylene. A sheet-like shape or a film shape of ethylene formate (PET), triallyl cyanurate (TAC), or epoxy. In addition, one type of the above-mentioned base materials may be used for the above-mentioned plastic base materials, and one or two or more laminated structures may be used.

Examples of the coating method for forming the coating film include a bar coating method, a spin coating method, a dip coating method, a gravure coating method, a spray coating method, a roll coating method, and a brush coating method.

[Optical member]

The optical member of the present embodiment includes the above-described transparent composite.

The optical member is not particularly limited as long as it can be used as a transparent plastic substrate, and examples thereof include a camera, a lens-attached film, and the like, and a film-integrated camera, a video camera, a car camera, and the like. Various camera lenses; CD, CD-ROM, MO, CD-R, CD-Video, DVD and other optical pickup (opticalpickup) lenses or microlens arrays, copiers, printers and other office automation machines, etc. Optical components of the machine or sheet, fiber optic communication device, LED Use a sealant or the like.

The method of mounting the transparent composite of the present embodiment to the optical member is not particularly limited, and may be carried out to the optical member by a conventional method.

As described above, the inorganic oxide transparent dispersion according to the present embodiment contains inorganic oxide particles modified by a surface modifier and having an average dispersed particle diameter of 1 nm or more and 50 nm or less, dissolves the resin, and hardly erodes the resin hardened. Since the highly polar solvent and the basic substance of the cured resin are used, even the inorganic oxide particles modified by the surface modifier can be well dispersed in a highly polar solvent.

According to the resin composition for forming a transparent composite of the present embodiment, since the resin is contained in the inorganic oxide transparent dispersion containing the surface-modified inorganic oxide particles, the highly polar solvent, and the basic substance, it is difficult to erode the surface modification. The inorganic oxide particles and the resin and the highly polar solvent of the cured resin obtained by curing the resin are uniformly mixed with the basic substance, so that a transparent composite can be formed without depending on the production conditions.

According to the transparent composite of the present embodiment, since the resin composition for forming a transparent composite is used, the surface-modified inorganic oxide particles can be uniformly dispersed in the resin to maintain the surface-modified inorganic oxide particles. Features and transparency.

According to the optical member of the present embodiment, since the transparent composite of the present embodiment is used, the characteristics of the surface-modified inorganic oxide particles and the transparency of the optical member can be maintained and imparted to the optical member.

(Example)

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention It is not limited to these embodiments.

[Example 1] [Production of Zirconium Oxide Particles]

In a solution of 2615 g of zirconium salt octahydrate hydrated zirconium chloride in 40 L of pure water, 344 g of 28% aqueous ammonia was dissolved in 20 L of pure water to prepare a zirconium oxide precursor slurry.

Next, in the slurry, a sodium sulfate aqueous solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added while stirring. The amount of sodium sulfate added at this time was 30% by mass based on the zirconium oxide equivalent value of zirconium ions in the zirconium salt aqueous solution.

Next, the mixture was dried in the air at 130 ° C for 24 hours using a dryer to obtain a solid matter. Next, the solid matter was pulverized by an automatic mortar, and then fired in the air at 500 ° C for 1 hour in an electric furnace to obtain a fired product.

Next, the fired product was placed in pure water and stirred to obtain a slurry, and then the slurry was washed with a centrifuge to sufficiently remove the added sodium sulfate to obtain a solid matter.

Thereafter, the solid matter was dried in the air at 130 ° C for 24 hours using a dryer to prepare zirconium oxide particles.

The average primary particle diameter of the zirconium oxide particles was measured by a field emission type electron microscope JEM-2100F (manufactured by JEOL Ltd.) to be 4 nm.

[Surface modification of zirconium oxide particles]

10 g of water was added to 10 g of the above zirconium oxide particles, and the mixture was stirred and mixed to prepare a transparent aqueous dispersion of zirconium oxide. Second, in the zirconium 5 g of 3-propenylmethoxypropyltrimethoxydecane KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface modifier was added to and mixed with the surface of the oxide transparent water dispersion to prepare the surface modification of the zirconium oxide particles. . Next, the surface-modified zirconium oxide particles were separated from water by solid-liquid separation, and dried using a dryer.

[Production of Zirconium Oxide Transparent Dispersion]

To 3 g of the surface-modified zirconium oxide particles described above, 7 g of isopropyl alcohol and 0.03 g of ammonia water having a concentration of 28% of a basic substance were added and stirred to obtain a zirconium oxide transparent dispersion.

Next, in order to measure the particle size distribution of the zirconium oxide in the zirconium oxide transparent dispersion, a dispersion in which the zirconium oxide particle content in the zirconium oxide transparent dispersion was adjusted to 1% by mass was prepared, and dynamic light scattering was used. The particle size distribution measuring apparatus (manufactured by Malvern Co., Ltd.) measures the particle size distribution of the zirconium oxide in the dispersion. Among them, the zirconium oxide has a refractive index of 2.15, and the isopropanol has a refractive index of 1.37. As a result, the volume-dispersed particle diameter (D50) at a cumulative volume fraction of the volume particle size distribution of the zirconium oxide particles of 50% by volume was 6 nm.

[Embodiment 2]

Except that 0.04 g of a 0.1 mol/L potassium hydroxide (KOH) isopropanol solution (containing about 19.4 mass% of water, manufactured by Kanto Chemical Co., Ltd.) was used instead of 0.03 g of ammonia water having a concentration of 28% as an alkaline substance. The same operation as in Example 1 was carried out to obtain a zirconium oxide transparent dispersion of Example 2.

The particle size distribution of the zirconium oxide in the zirconium oxide transparent dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 7 nm.

[Example 3]

The zirconium oxide transparent dispersion of Example 3 was obtained in the same manner as in Example 1 except that propylene glycol monomethyl ether (PGM) was used instead of isopropyl alcohol as the highly polar solvent.

The particle size distribution of the zirconium oxide in the zirconium oxide transparent dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 6 nm.

[Example 4] [Production of Titanium Oxide Particles]

In a titanium salt aqueous solution in which 2445 g of titanium trichloride was dissolved in 40 L of pure water, while stirring, a diluted ammonia water in which 28 g of 28% ammonia water was dissolved in 20 L of pure water was added to prepare a titanium oxide precursor slurry.

Next, in the slurry, an aqueous solution of sodium nitrate in which 300 g of sodium nitrate was dissolved in 5 L of pure water was added while stirring. The amount of sodium nitrate added at this time was 30% by mass based on the titanium oxide equivalent value of titanium ions in the titanium salt aqueous solution.

Next, the mixture was dried in the air at 130 ° C for 24 hours using a dryer to obtain a solid matter. Next, the solid matter was pulverized by an automatic mortar, and then fired in the air at 500 ° C for 1 hour in an electric furnace to obtain a fired product.

Next, the fired product was placed in pure water to be stirred into a slurry form, and then the slurry was washed with a centrifuge to sufficiently remove the added sodium nitrate to obtain a solid matter.

Thereafter, the solid matter was dried in the air at 130 ° C for 24 hours using a dryer to prepare titanium oxide particles.

The average primary particle diameter of the titanium oxide particles was measured by a field emission type electron microscope JEM-2100F (manufactured by JEOL Ltd.) to be 6 nm.

[Surface modification of titanium oxide particles]

The surface of the titanium oxide particles was subjected to the same operation as in Example 1, and surface modification was carried out using 3-propenyloxypropyltrimethoxydecane KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface modifying agent. Next, the surface-modified titanium oxide particles were separated from water by solid-liquid separation, and dried using a dryer.

[Production of titanium oxide transparent dispersion]

A titanium oxide transparent dispersion of Example 4 was obtained in the same manner as in Example 1 except that the surface-modified titanium oxide particles were used instead of the surface-modified zirconium oxide particles.

The particle size distribution of the titanium oxide in the titanium oxide transparent dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 8 nm.

[Comparative Example 1]

7 g of isopropyl alcohol was added to 3 g of the surface-modified zirconium oxide particles obtained in Example 1 and stirred to obtain a zirconium oxide dispersion liquid of Comparative Example 1 which did not contain a basic substance.

The particle size distribution of the zirconium oxide in the zirconium oxide dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 154 nm, and the dispersibility was inferior.

[Comparative Example 2]

The zirconium oxide dispersion of Comparative Example 2 was obtained in the same manner as in Example 1 except that methyl ethyl ketone (MEK) was used instead of isopropyl alcohol.

The particle size distribution of the zirconium oxide in the zirconium oxide dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 6 nm.

[Comparative Example 3]

The zirconium oxide dispersion of Comparative Example 3 was obtained in the same manner as in Example 1 except that 0.04 g of water was used instead of 0.03 g of 28% aqueous ammonia.

The particle size distribution of the zirconium oxide in the zirconium oxide dispersion was measured in the same manner as in Example 1, and the volume-dispersed particle diameter (D50) was 82 nm, and the dispersibility was inferior.

[Example 5] [Production of Resin Composition for Forming Transparent Composite]

5 g of the zirconium oxide transparent dispersion obtained in Example 1, 5 g of an acrylic resin PET-30 (manufactured by Nippon Kayaku Co., Ltd.), and 1-[4-(2-hydroxyethoxy) as a photopolymerization initiator 0.01 g of -phenyl]-2-hydroxy-2-methyl-1-propan-1-ol IRGACURE 2959 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed to obtain a resin composition for forming a transparent composite of Example 5.

[Embodiment 6]

The transparent composite forming resin of Example 6 was obtained in the same manner as in Example 5 except that the zirconium oxide transparent dispersion obtained in accordance with Example 2 was used instead of the zirconium oxide transparent dispersion obtained in Example 1. Composition.

[Embodiment 7]

In addition to using the zirconium oxide transparent dispersion obtained in accordance with Example 3, in place of the zirconium oxide transparent dispersion obtained in accordance with Example 1, In the same manner as in Example 5, the resin composition for forming a transparent composite of Example 7 was obtained.

[Embodiment 8]

A transparent composite forming resin of Example 8 was obtained in the same manner as in Example 5 except that the titanium oxide transparent dispersion obtained in accordance with Example 4 was used instead of the zirconium oxide transparent dispersion obtained in accordance with Example 1. Composition.

[Comparative Example 4]

A resin composition for forming a composite of Comparative Example 4 was obtained in the same manner as in Example 5 except that the zirconium oxide dispersion liquid obtained in Comparative Example 1 was used instead of the zirconium oxide transparent dispersion obtained in Example 1.

[Comparative Example 5]

A resin composition for forming a composite of Comparative Example 5 was obtained in the same manner as in Example 5 except that the zirconium oxide dispersion liquid obtained in Comparative Example 2 was used instead of the zirconium oxide transparent dispersion obtained in accordance with Example 1. .

[Comparative Example 6]

A resin composition for forming a composite of Comparative Example 6 was obtained in the same manner as in Example 5 except that the zirconium oxide dispersion liquid obtained in Comparative Example 3 was used instead of the zirconium oxide transparent dispersion obtained in accordance with Example 1. .

[Embodiment 9] [Production of transparent composite]

The resin composition for forming a transparent composite obtained in Example 5 was applied onto a polycarbonate substrate by a bar coating method to form a coating film. Then, the polycarbonate substrate with the coating film was dried in an electric furnace at 60 ° C for 5 minutes, and then irradiated with ultraviolet rays by a high pressure mercury lamp to cure the resin in the coating film to obtain a transparent composite having a thickness of 30 μm.

Next, the light transmittance of the transparent composite was measured using a spectrophotometer V-570 (manufactured by JASCO Co., Ltd.), that is, the light transmittance of the entire polycarbonate substrate and the coating film was measured.

The measurement results are shown in Fig. 2.

According to Fig. 2, the transmittance for light having a wavelength of 400 nm is 91%.

[Embodiment 10]

The same procedure as in Example 9 was carried out except that the resin composition for forming a transparent composite obtained in Example 6 was used instead of the resin composition for forming a transparent composite obtained in Example 5, and the thickness of Example 10 was 30 μm. Transparent composite.

Next, the light transmittance of the transparent composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was 90%.

[Example 11]

The thickness of 30 μm of Example 11 was obtained in the same manner as in Example 9 except that the resin composition for forming a transparent composite obtained in Example 7 was used instead of the resin composition for forming a transparent composite obtained in Example 5. Transparent composite.

Next, the light transmittance of the transparent composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was 91%.

[Embodiment 12]

The thickness of Example 12 was obtained in the same manner as in Example 9 except that the resin composition for forming a transparent composite obtained in Example 8 was used instead of the resin composition for forming a transparent composite obtained in Example 5. 30 μm transparent composite.

Next, the light transmittance of the transparent composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was 92%.

[Comparative Example 7]

The thickness of the comparative example 7 was 30 μm, except that the resin composition for forming a composite body obtained in Comparative Example 4 was used instead of the resin composition for forming a transparent composite obtained in Example 5, except that the same procedure as in Example 9 was carried out. The complex.

Next, the light transmittance of the composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was as low as 12%. This is considered to be because the zirconium oxide particles in the highly polar solvent have poor dispersibility, and therefore the zirconium oxide particles aggregate with each other to lower the transparency of the composite.

[Comparative Example 8]

The same procedure as in Example 9 was carried out except that the resin composition for forming a composite obtained in Comparative Example 5 was used instead of the resin composition for forming a transparent composite obtained in Example 5, and the thickness of Comparative Example 8 was 30 μm. The complex.

Next, the light transmittance of the composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was as low as 75%. This can be considered as a polycarbonate substrate eroded by methyl ethyl ketone (MEK), so the polycarbonate substrate is not transparent Caused by.

[Comparative Example 9]

The same procedure as in Example 9 was carried out except that the resin composition for forming a composite obtained in Comparative Example 6 was used instead of the resin composition for forming a transparent composite obtained in Example 5, and the thickness of Comparative Example 9 was 30 μm. The complex.

Next, the light transmittance of the composite was measured in accordance with Example 9, and the transmittance for light having a wavelength of 400 nm was as low as 75%.

This is considered to be because the zirconium oxide dispersion is prepared by using water instead of 28% ammonia water. Therefore, the dispersibility of the zirconium oxide particles in the highly polar solvent is poor, and thus the dispersibility of the zirconium oxide particles of the obtained composite is lowered.

From the above, it was confirmed that in order to satisfactorily disperse the surface-modified zirconium oxide particles having a reduced surface polarity in a highly polar solvent, it is not necessary to require water and a basic substance is required.

(industrial availability)

The present invention is suitable for use as an inorganic oxide as an organic resin filler, and can be suitably used for: an inorganic oxide transparent dispersion which maintains transparency of a resin while improving optical and mechanical properties of the resin; A resin composition for forming a transparent composite of a dispersion and a resin; a transparent composite formed using the resin composition for forming a transparent composite; and an optical member including the transparent composite.

1‧‧‧Inorganic oxide particles

2‧‧‧decane coupling agent

3‧‧‧Alkaline substances

Fig. 1 is a view showing the action of a basic substance in the inorganic oxide transparent dispersion of the present invention.

Fig. 2 is a view showing the results of measurement of the light transmittance of the transparent composite of Example 9 of the present invention.

The diagram of this case is a schematic diagram of the action of the alkaline substance in the transparent dispersion of inorganic oxide and the result of measuring the light transmittance. However, the first item in the request of the present case is an inorganic oxide transparent dispersion, so the illustration is insufficient.矣 represents the technical characteristics of this case.

Claims (7)

An inorganic oxide transparent dispersion containing inorganic oxide particles modified by a surface modifier and having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a resin which dissolves the resin and which is less likely to erode the hardened resin which is hardened by the foregoing resin a highly polar solvent and a basic substance; the high-polarity solvent is any one or two of an alcohol and an ether, the inorganic oxide particles are tetragonal zirconia ZrO ₂ , and the high-polar solvent is isopropyl alcohol. And either or both of propylene glycol monomethyl ether, the alkaline substance being ammonia. The inorganic oxide transparent dispersion liquid according to the first aspect of the invention, wherein the content of the basic substance is 0.01% by mass or more and 10% by mass or less based on the total amount of the inorganic oxide particles. The inorganic oxide transparent dispersion according to claim 1, wherein a composite having a thickness of 30 μm formed of the resin composition containing the inorganic oxide transparent dispersion and the resin is used in the visible light field at 400 nm. The transmittance in the wavelength region to 800 nm is 80% or more. The inorganic oxide transparent dispersion according to claim 1, wherein the surface modifier is a decane coupling agent. A resin composition for forming a transparent composite, which comprises the inorganic oxide transparent dispersion according to any one of claims 1 to 4, and a resin. A transparent composite formed by using a resin composition for forming a transparent composite according to claim 5 of the patent application. An optical member comprising the transparent composite according to claim 6 of the patent application.